Alkyl-hydroxamic acids and salts thereof as anti-fungal agents

ABSTRACT

THE USE OF ALKYL-HYDROXAMIC ACIDS OR THEIR SALTS IN THE TREATMENT OF SURFACES SUCH AS FABRIC, SKIN HIDES, WOOD, METAL, AND PLASTIC FOR THE PURPOSE OF PROVIDING AN ANTIFUNGAL FINISH TO THE SURFACES. THESE COMPOUND ARE PREPARED BY THE REACTION OF THE CORRESPONDING CARBOXYLIC ESTER WITH HYDROXYLAMINE.

ALKYL-HYDROXAMIC ACIDS AND SALTS THEREOF AS ANTI-FUNGAL AGENTS Reginald L. Wakeman, Philadelphia, Pa., and Edward Gritiin Shay, Belle Mead, N.J., assignors to Millrnaster Onyx Corporation, New York, NY.

No Drawing. Continuation-impart of abandoned applica tion Ser. No. 375,356, June 15, 1964. This application Dec. 15, 1969, Ser. No. 885,372

Int. Cl. A01n 9/38 US. Cl. 424291 3 Claims ABSTRACT OF THE DISCLOSURE The use of alkyl-hydroxamic acids or their salts in the treatment of surfaces such as fabL C, skin, hides, wood, metal, and plastic for the purpose of providing an antifungal finish to the surfaces. These compounds are prepared by the reaction of the corresponding carboxylic ester with hydroxylamine.

This is a continuation-in-part of co-pending application Ser. No. 375,356, filed June 15, 1964 now abandoned.

This invention relates to a process for treating surfaces to impart fungicidal or fungistatic properties. It is especially concerned with the treatment of surfaces with a durable, water-resistant finish which will. provide protection for the surface without any undesirable side effects.

The prevention of deterioration of various substrates by treatment with'fungicidal agents is not new, but most of the agents now used have one or more drawbacks. Materials now used for the treatment of surfaces may impart undesirable color or odor; they may be required in large amounts; they may have undesirable toxicological properties or they may be readily removed by washing.

It is an object of the present invention to provide a process for treating surfaces which is largely free from the above mentioned disadvantages. For example, this process produces on fabric, yarn or thread and the like a surface which is not readily attached by fungus organisms. This process imparts to objectionable color, odor or hand to fabric, yarn or thread and the treated material retains anti-fungal properties through many washings.

The above objects are accomplished through the use of alkyl hydroxamic acids or their salts in the treatment of surfaces. These substances, in relatively low concentrations, are capable of imparting an excellent and relatively permanent anti-fungal finish to various surfaces including fabric, skin, hides, wood, metal and plastic.

In addition, these compounds are biologically compatible with a variety of other surface treatment agents including paint, soap, solvents and the like to facilitate treatmeii't of a diversity of surfaces.

The compounds used in this process can be represented by the formula:

thesis. Among the metal salts utilizable for this purpose 3,632,764 Patented Jan. 4, 1972 EXAMPLE I In a 1,000 ml. beaker, 70 grams of hydroxylamine hydrochloride were dissolved in 360 cc. of methanol by heating. In a 500 ml. beaker, 84.5 grams of potassium hydroxide were dissolved in 210 cc. of methanol. Both solutions were cooled to room temperature. The liter beaker containing the hydroxylamine hydrochloride was placed in an ice bath and, with stirring, the potassium hydroxide solution was slowly added. The potassium chloride which precipitated was filtered off in a vacuum filtration and the filtrate placed in a screw-cap, 32 ounce jar. To this were added 99 grams of methyl undecylenate. The jar was sealed, shaken and allowed to stand at room temperature one hour. The precipitate which formed was filtered, water washed and dried to give 88.8 grams yield) of white crystals of potassium undecylenyl hy= droxamate. Instead of potassium hydroxide, sodium hydroxide may be substituted in equivalent amount.

EXAMPLE 11 One inch squares of cotton fabric were treated with the following compounds to give 1% by weight of each compound on the fabric: potassium undecylenyl hydroxamate, potassium undecylenate, undecylenic acid, undecylenyl alcohol, and methyl undecylenate.

Each of these cotton squares was then placed in an agar plate and inoculated with Aspergillus nigcr. These plates were stored at 30 C. and relative humidity for 7 days. At the end of that time, each of the swatches 2-5 had completely grown over with the organism. Swatch 1 had no growth on the fabric and showed an average zone of inhibition of 1.5 mm.

EXAMPLE III Using the technique of Example I, the following methyl esters were converted to the corresponding hydroxamic acids in the yields shown:

1 A pro duct of the Shell Chemical Com any. New York, N.Y. Versatic Acid 9-11 is a mixture of highly branched principally tertiary carboxylic acids containing from 9 to 11 carbon atoms.

Each of the hydroxamic acids from esters A-K was used to treat one inch cotton squares at 1% by weight. These swatches were inoculated and incubated as in Example II. The only compounds affording any protection were B-F with D, E and F giving the best resistance to fungal growth.

EXAMPLE IV Potassium undecylenyl hydroxamate was dissolved in butyl Cellosolve at 5% and this solution combined with an uninhibited latex base paint to give a 0.5% level of fungicide. Filter paper swatches were coated with this paint and inoculated in agar plates with Pullularia pullulans for two weeks at 28 C. and 95% relative humidity. No fungal growth was noted on the treated paint swatches at the end of this time.

EXAMPLE V Approximately 12 grams of potassium undecylenyl hydroxamate were dissolved in 500 cc. of 50:50 isopropanol:water and 8 grams of mercuric acetate dissolved in 100 grams of distilled water added. The mixture was heated briefly on a'steam bath and the precipitate which formed separated and dried to give 12.8 grams (86% yield) of mercuric undecylenyl hydroxamate, a light yellow sticky paste.

EXAMPLE VI In the same manner as in Example V, the silver salt of undecylenyl hydroxamate is prepared by substituting 8.5 grams of silver acetate for the mercuric acetate of that example.

EXAMPLE VII Cupric undecylenyl hydroxamate is prepared by substituting 10 grams of cupric acetate monohydrate for the mercuric acetate of Example V.

EXAMPLE VIII The corresponding barium, calcium, magnesium, strontium and zinc undecylenyl hydroxamates are prepared in the same manner, by metathesis with equivalent amounts of the acetates of the corresponding metals. Salts of other acids may be used for this purpose, provided that their potassium or sodium salts are soluble in the reaction medium.

4 The invention claimed is: 1. A process for killing fungi on solid surfaces comprising applying to said fungi a fungicidal amount of a compound having the structure:

References Cited FOREIGN PATENTS 742,812 1/1956 Great Britain 424-291 JEROME D. GOLDBERG, Primary Examiner V. D. TURNER, Assistant Examiner US. Cl. X.R. 

